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Bulletin of Volcanology

, Volume 69, Issue 3, pp 319–328 | Cite as

Surface alteration of basalt due to cation-migration

  • Dorothee J. M. BurkhardEmail author
  • Hiltrud Müller-Sigmund
Research Article

Abstract

Basaltic lava from Kilauea, Hawaii may have a red-brown surface, indicative of Fe-(hydr)oxides. This surface is not found where exposed to weathering, but at the interface between lava lobes, or in the interior of lava channels. We use several analytical techniques to determine how these Fe-(hydr)oxide surfaces may have developed. WDS-elemental distribution line profiles from the lava surface towards the lava´s interior detect an Fe-rich film of less than 5 μm thickness. Heat treatment of quenched, fresh lava samples of the same chemical composition between 600–1,090°C helps to replicate temperatures under which such an Fe-rich film might have formed. These experiments suggest that Fe-enrichment occurs above 1,020°C, whereas at lower temperatures Ca is enriched relative to Fe. One sample was treated below the glass transition temperature, at 600°C for 164 h. A depth profile with secondary neutral mass spectrometry shows an enrichment of Mg at the outer 50 nm of the glass surface. The formation of films requires cation migration, which is driven by an oxygen chemical potential between air and the reduced basalt (Fe2+/Fe3+ ratio of 13.3). The change of surface alteration from Mg to Ca film at lower temperatures, to predominantly Fe at high temperatures, is determined by a change of cation availability, largely controlled by crystallization that already occurs below 850°C, and volume crystallization that occurs above 925°C.

Keywords

Surface-alteration Basalt (glass) Cation transport Oxygen potential Kilauea, Hawaii 

Notes

Acknowledgements

The work was initiated during a field trip DJMB enjoyed on the lava fields of Pu`u O`o in December 1998 with Carl Thornber who was at that time at the USGS Hawaiian Volcano Observatory (HVO). DJMB thanks Don Swanson from HVO for logistical help. We appreciate the kind offer by Jim Kauahikaua, HVO, for the use of a photograph (Fig. 1) which demonstrates best the phenomena discussed in this paper. The authors thank M. Sommer, Institute for Instrumental Analytics, Karlsruhe Research Centre for the taking an SNMS depth profile. Harald Behrens, University of Hannover, Germany, provided valuable comments on an earlier version of the manuscript. The authors thank an anonymous reviewer and especially RF Cooper for critical and supportive comments.

References

  1. Burkhard DJM (2001) Crystallization and oxidation of Kilauea basalt glass: processes during reheating experiments. J Petrol 42:507–527CrossRefGoogle Scholar
  2. Burkhard DJM (2002) Kinetics of crystallization: example of micro-crystallization in basalt lava. Contrib Mineral Petrol 142:724–737Google Scholar
  3. Burkhard DJM (2003) Thermal Interaction between lava lobes. Bull Volcanol 65:136–143Google Scholar
  4. Burkhard DJM (2005a) Relation between oxidation/crystallization and degassing upon reheating of basalt glass from Kilauea, Hawaii. Mineral Mag 69:103–117CrossRefGoogle Scholar
  5. Burkhard DJM (2005b) Nucleation and growth rates of pyroxene, plagioclase and Fe-Ti oxides in basalt under atmospheric conditions. Eur J Mineral 17:675–685CrossRefGoogle Scholar
  6. Burkhard DJM, Scherer T (2006) Surface oxidation of basalt glass/liquid. J Non-Crystal Solids 352:241–247. DOI 10.1016/j.jnoncrysol.2005.11.029 CrossRefGoogle Scholar
  7. Cooper RF, Fanselow JB, Weber JKR, Merkley DR, Poker DB (1996a) Dynamics of oxidation of a Fe2+-bearing aluminosilicate (basaltic) melt. Science 274:1173–1176CrossRefGoogle Scholar
  8. Cooper RF, Fanselow JB, Poker DB (1996b) The mechanism of oxidation of a basaltic glass: chemical diffusion of network-modifying cations. Geochim Cosmochimica Acta 60:3253–3265CrossRefGoogle Scholar
  9. Cook GB, Cooper RF (2000) Iron concentration and the physical processes of dynamic oxidation in an alkaline earth aluminosilicate glass. Am Mineral 85:397–406Google Scholar
  10. Cook GB, Cooper RF (1999) Redox dynamics in the float-processing of glasses I: Reaction between undoped and iron-doped borosilicate glassmelts and a gold-tin alloy. J Non-Crys Solids 249:210–227CrossRefGoogle Scholar
  11. Cook GB, Cooper RF, Wu T (1990) Chemical diffusion and crystalline nucleation during oxidation of ferrous-bearing magnesium aluminosilicate glass. J Non-Crystal Solids 120:207–222CrossRefGoogle Scholar
  12. Dutton CE (1884) Hawaiian volcanoes, US Geological Survey 4th Annual Report, USGS, Reston, VA, pp 75–219Google Scholar
  13. Everman RLA, Cooper RF (2003) Internal reduction of an iron-doped magnesium aluminosilicate melt. J Am Ceram Soc 86:484–494CrossRefGoogle Scholar
  14. Fegley B, Klingelhofer G, Brackett RA, Izenberg N, Kremser DT, Lodders K (1995) Basalt oxidation and the formation of hematite on the surface of Venus. Icarus 118:373–383CrossRefGoogle Scholar
  15. Goschnick J, Natzeck C, Sommer M, Zudock F (1998) Depth profiling of non-conductive oxide multilayers with plasma-based SNMS in HF-mode. Thin Solid Films 332:215–219CrossRefGoogle Scholar
  16. Helz RT, Thornber C (1987) Geothermometry of Kilauea Iki lava lake, Hawaii. Bull Volcanol 49:651–668CrossRefGoogle Scholar
  17. Hofmann S (1998) Sputter depth profile analysis of interfaces. Rep Prog Phys 61:827–888CrossRefGoogle Scholar
  18. Johnson N, Fegley B (2002) Experimental studies of atmosphere-surface interactions on Venus. Planet Atmosph Adv Space Res 29:233–241CrossRefGoogle Scholar
  19. Joy D (1995) Monte Carlo modelling for electron microscopy and microanalysis. Oxford University Press, New YorkGoogle Scholar
  20. Keszthelyi L (1995) Measurements of the cooling at the base of pahoehoe flows. Geophys Res Lett 22:21–2198CrossRefGoogle Scholar
  21. Keszthelyi L, Denlinger R (1996) The initial cooling of pahoehoe flow lobes. Bull Volcanol 58:5–18CrossRefGoogle Scholar
  22. Lockwood JP, Lipman PW (1987) Holocene eruptive history of Mauna Loa volcano. In: Decker RW, Wright TL, Stauffer PH (eds) Volcanism in Hawaii 1, US Geol Surv Prof Pap 1350:509–535, USGS, Reston, VAGoogle Scholar
  23. Minitti ME, Mustrad JF, Rutherford MJ (2002) Effects of glass content and oxidation on the spectra of SNC-like baslts: applications to Mars remote sensing. J Geophys Res 107. DOI 10.1029/2001JE001518
  24. Minitti M, Lane MD, Bishop JL (2005) A new hematite formation mechanism for Mars. Meteoritics Planet Sci 40:55–59CrossRefGoogle Scholar
  25. Mysen BO, Virgo D, Seifert F (1984) Redox equilibria of iron in alkaline earth silicate melts: relationships between melt structure, oxygen fugacity, temperature and properties of iron-bearing silicate liquids. Am Mineral 69:834–847Google Scholar
  26. Oechsner H (1984) Thin film and depth profile analysis. In: Oechsner H (ed) Topics in current physics 34. Springer, Berlin Heidelberg New YorkGoogle Scholar
  27. Philpotts AR (1990) Principles of igneous and metamorphic petrology. Prentice Hall, Englewood Cliffs, New JerseyGoogle Scholar
  28. Schmalzried H (1983) Internal and external oxidation of nonmetalic compounds and solid solutions (I). Ber Bunsen-Gesellsch Physik Chemie 87:551–558Google Scholar
  29. Seymond RB, Mizutani Y, Briggs PH (1996) Long-term geochemical surveillance of fumaroles at Shiowa-Shinzan dome, Usu volcano, Japan. J Volcanol Geothermal Res 73:177–211CrossRefGoogle Scholar
  30. Smith DR, Cooper RF (2000) Dynamic oxidation of a Fe2+-bearing calcium-magnesium-aluminosilicate glass: the effect of molecular structure on chemical diffusion and reaction morphology. J Non-Crystal Solids 278:145–163CrossRefGoogle Scholar
  31. White AF, Hochella MF (1992) Surface chemistry associated with the cooling and subaerial weathering of recent basalt flows. Geoch Cosmochimica Acta 56:3711–3721CrossRefGoogle Scholar
  32. Zambonini F, Carrobbi G (1927) A chemical study of the yellow incrustations on the Vesuvian lava of 1631. Am Mineral 12:1–10Google Scholar

Copyright information

© Springer-Verlag 2006

Authors and Affiliations

  • Dorothee J. M. Burkhard
    • 1
    • 2
    Email author
  • Hiltrud Müller-Sigmund
    • 3
  1. 1.Institute for Technical Chemistry, Water and Geotechnology (ITC-WGT)Forschungszentrum KarlsruheKarlsruheGermany
  2. 2.Institute for Mineralogy and GeochemistryUniversity of KarlsruheKarlsruheGermany
  3. 3.Institute of Mineralogy, Petrology and GeochemistryUniversity of FreiburgFreiburgGermany

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